A very rare hydrogen-bridged hexanuclear CuII complex containing a triangular Cu3O core capped by an unusual triply coordinated perchlorate anion

An unusual hexanuclear Cu-II complex, [{[Cu(NHDEPO)](3)(mu(3)-O)(O3ClO)}(2)(mu-H)]center dot 7ClO(4)center dot 4H(2)O (1) was prepared starting from Cu(ClO4)(2)center dot 6H(2)O and the oxime-based Schiff base ligand NHDEPO (= 3-[3-(diethylamino)propylimino]butan-2-one oxime). Structural characterization of the complex reveals that it consists of two triangular Cu3O units, the copper ions being at the corners of an equilateral triangle, separated by an O center dot center dot center dot O distance of 2,447(5) angstrom, held together solely by a proton. In each triangle, the copper atoms are in square-pyramid environments. The equatorial plane consists of the bridging oxygen of the central OH-(O2-) group together with three atoms (N, N, O) of the Schiff base. All Unusual triply coordinated perchlorate ion (mu(3)-kappa O:kappa O':kappa O '') interacts in axial position with the three copper ions, Variable-temperature (2-300 K) magnetic susceptibility measurements show that complex 1 is antiferromagnetically Coupled (J = -148 cm(1-)). The EPR data at low temperature clearly indicates the presence of spin frustration phenomenon in the complex.

Dimorphosim of a dimethoxy bridged oxovanadium(v)-hydrazone complex

A monoclinic variety with C2/c space group of the title complex [(VO)-O-V(L)(OCH3)](2), incorporating the doubly deprotonated benzoyl hydrazone of 2-hydroxy-5-methylacetophenone (H2L) was synthesized from the decomposition of [(VO)-O-IV(L)(bipy)] (where bipy representing the 2,2'-bipyridine) in methanol which has been reported very recently from our laboratory In this paper we report another monoclinic variety of this complex with P2(1)/n space group that showed some differences in bonding patterns in the solid state (but in solution they are almost identical) prepared by different synthetic method viz, from the equimolar reaction of [(VO)-O-IV(acac)(2)], H2L and imidazole in CH3OH.

Synthesis, characterization and molecular structure of 1,1′ bis(diphenylphosphino ferrocene)dioxide complex of uranyl nitrate

A 1,1' bis(diphenylphosphino ferrocene) dioxide complex of uranyl nitrate was synthesized and characterized by IR, H-1 and P-31{H-1} NMR spectroscopic and X-ray diffraction methods. The structure of the compound shows that the uranium atom is surrounded by eight oxygen atoms in a hexagonal bi-pyramidal geometry. Two oxygen atoms from 1,1' bis(diphenylphosphino ferrocene) dioxide ligand and four oxygen atoms from the nitrate groups form a planar hexagon. The two uranyl oxygen atoms occupy the axial position. The 1,1' bis(diphenylphosphino ferrocene) dioxide ligand acts as a bidentate chelating ligand with a bite angle of 71.56(8)degrees around the uranium(VI) atom, which is much smaller in value compare to any of the previously reported values (90.1 degrees-154.0 degrees) for this ligand.

Fast regridding of large, complex geospatial datasets

In the earth sciences, data are commonly cast on complex grids in order to model irregular domains such as coastlines, or to evenly distribute grid points over the globe. It is common for a scientist to wish to re-cast such data onto a grid that is more amenable to manipulation, visualization, or comparison with other data sources. The complexity of the grids presents a significant technical difficulty to the regridding process. In particular, the regridding of complex grids may suffer from severe performance issues, in the worst case scaling with the product of the sizes of the source and destination grids. We present a mechanism for the fast regridding of such datasets, based upon the construction of a spatial index that allows fast searching of the source grid. We discover that the most efficient spatial index under test (in terms of memory usage and query time) is a simple look-up table. A kd-tree implementation was found to be faster to build and to give similar query performance at the expense of a larger memory footprint. Using our approach, we demonstrate that regridding of complex data may proceed at speeds sufficient to permit regridding on-the-fly in an interactive visualization application, or in a Web Map Service implementation. For large datasets with complex grids the new mechanism is shown to significantly outperform algorithms used in many scientific visualization packages.

Modeling of complex-valued Wiener systems using B-spline neural network

In this brief, a new complex-valued B-spline neural network is introduced in order to model the complex-valued Wiener system using observational input/output data. The complex-valued nonlinear static function in the Wiener system is represented using the tensor product from two univariate B-spline neural networks, using the real and imaginary parts of the system input. Following the use of a simple least squares parameter initialization scheme, the Gauss-Newton algorithm is applied for the parameter estimation, which incorporates the De Boor algorithm, including both the B-spline curve and the first-order derivatives recursion. Numerical examples, including a nonlinear high-power amplifier model in communication systems, are used to demonstrate the efficacy of the proposed approaches.

Spectro-electrochemical and DFT studies of a planar Cu(II)–phenolate complex active in the aerobic oxidation of primary alcohols

A square-planar compound [Cu(pyrimol)Cl] (pyrimol = 4-methyl-2-N-(2-pyridylmethylene)aminophenolate) abbreviated as CuL–Cl) is described as a biomimetic model of the enzyme galactose oxidase (GOase). This copper(II) compound is capable of stoichiometric aerobic oxidation of activated primary alcohols in acetonitrile/water to the corresponding aldehydes. It can be obtained either from Hpyrimol (HL) or its reduced/hydrogenated form Hpyramol (4-methyl-2-N-(2-pyridylmethyl)aminophenol; H2L) readily converting to pyrimol (L-) on coordination to the copper(II) ion. Crystalline CuL–Cl and its bromide derivative exhibit a perfect square-planar geometry with Cu–O(phenolate) bond lengths of 1.944(2) and 1.938(2) Å. The cyclic voltammogram of CuL–Cl exhibits an irreversible anodic wave at +0.50 and +0.57 V versus ferrocene/ferrocenium (Fc/Fc+) in dry dichloromethane and acetonitrile, respectively, corresponding to oxidation of the phenolate ligand to the corresponding phenoxyl radical. In the strongly donating acetonitrile the oxidation path involves reversible solvent coordination at the Cu(II) centre. The presence of the dominant CuII–L. chromophore in the electrochemically and chemically oxidised species is evident from a new fairly intense electronic absorption at 400–480 nm ascribed to a several electronic transitions having a mixed pi-pi(L.) intraligand and Cu–Cl -> L. charge transfer character. The EPR signal of CuL–Cl disappears on oxidation due to strong intramolecular antiferromagnetic exchange coupling between the phenoxyl radical ligand (L.) and the copper(II) centre, giving rise to a singlet ground state (S = 0). The key step in the mechanism of the primary alcohol oxidation by CuL–Cl is probably the alpha-hydrogen abstraction from the equatorially bound alcoholate by the phenoxyl moiety in the oxidised pyrimol ligand, Cu–L., through a five-membered cyclic transition state.

Conformational polymorphism of the molecular complex of 3-fluorobenzoic acid with 4-acetylpyridine

Two polymorphs of the molecular complex formed between 3-fluorobenzoic acid with 4-acetylpyridine are described and found to be based upon the same dimeric supramolecular construct. The conformational freedom around the hydrogen bond results in a 180 degrees rotation about this intermolecular link, distinguishing the polymorphs and affecting the packing of the dimeric units. The two polymorphs are fully characterised by single crystal X-ray and neutron diffraction and quantum mechanical calculations. There is evidence of structured crystal growth defects in both polymorphic crystals via observation of diffuse scattering and a disorder model for the average structure of Form I, which can be interpreted as a mixing of the two dimer conformations. The similarity of energy of the distinct dimeric units, supporting their likely co-existence, has been verified by periodic quantum chemical calculations.

Structure determination of an intercalating ruthenium dipyridophenazine complex which kinks DNA by semiintercalation of a tetraazaphenanthrene ligand

We describe a crystal structure, at atomic resolution (1.1 Å, 100 K), of a ruthenium polypyridyl complex bound to duplex DNA, in which one ligand acts as a wedge in the minor groove, resulting in the 51° kinking of the double helix. The complex cation Λ-[Ru(1,4,5,8-tetraazaphenanthrene)2(dipyridophenazine)]2+ crystallizes in a 1∶1 ratio with the oligonucleotide d(TCGGCGCCGA) in the presence of barium ions. Each complex binds to one duplex by intercalation of the dipyridophenazine ligand and also by semiintercalation of one of the orthogonal tetraazaphenanthrene ligands into a second symmetrically equivalent duplex. The result is noncovalent cross-linking and marked kinking of DNA.